Diazotizable azodyestuffs



Patented May 19, 1942 DIAZOTIZABLE AZODYESTUFFS Fritz Suckfiill, Ieverkusen-Wiesdori, and Heinrich Ciingestein, Cologne-on-the-Bhine, Germany, assignors to General Aniline I; Film Corporation, a corporation of Delaware No Drawing. Original application March 9, 1938,

Serial No. 194,833.

Divided and this application November ,7, 1940, Serial No. 364,670. In Germany March 17, 1937 3Claims.

The present invention relates to new diazotizable azodyestuifs, to a method of preparing the same, to a process ofdyeing and to dyed fibers; more particularly it relates to diazotizable yellow azodyestufis which may be represented by the general formula:

In this formula G stands for the radical of a yellow component or several yellow components which are connected by azo groups, G being free from diazotizable amino groups, Y stands for a negativating substituent.-

Our new dyestuffs are obtainable by causing arylene diamines which may contain solubilizing groups to react on one side with an aroyl halide containing in the aryl nucleus besides a substituent being convertible into the amino group,

such as 9. nitro group or an ac'ylamino group, a negativating substituent, diazotizing the free halides of the following formula:

22 I C0.halogeu Y wherein X stands for substituent being convertible into the amino group, such as a nitro group or an acylamino group and Y stands for a negativating substituent, as, for instance, CN, 402-, CO, NOz, or halogen; the divalent substituents SO2 and -CO have one bond attached to the aryl nucleus, while the other bond may carry any radical. Such halides are, for instance, cyanonitrobenzoyl. chlorides, monoor dihalogen-nitro-benzoyl chlorides, dinitrobenzoyl chlorides, the acid chlorides of nitrophen'ylalkylsulfone carboxylic acids and so on.

As suitable yellow components for our new dyestuils may be mentioned by way of example pyrazolone s, acetoacetic arylides, ketoles, phenol,-

o-carboxylic acids or the derivatives or substitu- 1 tion products thereof.

Our new dyestuffs show in contrast to the known dyestuffs, which do not containthe negativating substituent in the amino aroyl radical the advantage, when diazotized on the fiber and developed with p-naphthol, of yielding yellower shades. The diazotizable dyestuiis used until now for yellow shades had to be developed with. pyrazolones in order to obtain the yellow shade, for, when developed with p-naphthoLthese dyestufls yield red to orange shades. The technical advantage of the present dyestuffs becomes chiefly evident in shading, as in the dyeing practice mostly'not the pure diazotizable dyestuil's but mixtures of the same are used, in order to obtain different shades in different directions, such asfashion shades and so on. Although most of the diazotizable dyestuffs are developed with p-naphthol a yellow-shading was not possible with dyestufls of the p-naphthol-series up to the present. The known yellow diazotizable dyestuffs had, without exception, to be developed withpyrazolone as already mentioned above, and therefore they were not suitable for shading in the "p-naphthol series. Only such a diazotizable dyestui! can be suitable for this purpose which yields developed with p-naphthol yellow shades, since it is practically'not possible to develop either successively or simultaneously with pnaphthol and pyrazolone. In some cases it was possible to shade with orange instead of yellow, however, the reddish tinge shown by the dyeings thus produced, mostly proved very undesirable.

' Owing to this quite a number of shades wanted could not be obtaiend. In the dyeing practice therefore the ardent want existed for diazotizable dyestufls which can be developed to yellower shades with p-naphthol andwith which yellowshading can be carried out without dimculties. For the first time diazotizable dyestuifs of this kind are disclosed by the present invention: they meet a long felt want and therefore represent a remarkable and important advance in the art.

This application is a divisional of our co-pending earlier application Serial No.'194,833,' filed March 9, 1938 now Patent No. 2,228,290, issued amine are diazotized with 69 parts of sodium nitrite and 320 parts of hydrochloric acid (19.5 B.); the diazo compound thus obtained is run into a solution prepared from 140 parts of salicylic acid'and 300 parts of sodium carbonate. When the coupling is complete the dyestuif thus formed is treated at 55 C. with 420 parts of crystallized sodium Sulfide until one nitro group is reduced to theamino group; the dyestufl. is isolated by adding salt. It corresponds in its free state to the following formula: v

H. N=N NH.COC 0011 NH:

and dyes cotton yellow shades; after diazotization and developing with fl-naphthol essentially yellower shades are obtained than with the corresponding reduced dyestuflf prepared from mnitro-benzoy1-p-phenylenediamine, which only diifers from the first dyestuif by the absence of the nitro group.

Example 2 188 parts of the 1,3-phenylenediamine-4-sulfonic acid are dissolved in water to a neutral solution and treated-in the presence of an acid binding agent-at 90 C. with 300 parts of the chloride of 4-carboxy-2-nitrophenyl-methyl-sulfone. After cooling, the condensation product of the constitution:

W WOGWH.

and 280 parts of sodium carbonate, after the coupling is complete the nitro group is reduced with 420 parts of crystallized sodium sulfide to the amino group. The dyestuff obtained corresponds in its free state to the following formula:

Hac-

and yields on cotton after diazotization and developing with p-naphthol a distinctly yellower shade than when using the condensation product of the constitution:

NO: NaOJsQNELCOO which does not contain the negative substituent.

(5n. nmsQmrco Example 3 437 parts of the condensation product obtained according to Example 2, paragraph 1, are diazotized and. united with 220 parts of m-aminophenylpyrazolone-3-carboxylic acid and 280 parts of sodium carbonate. The isolated monoazodyestufl is further diazotized with 75 parts of sodium nitrite and 500 parts of hydrochloric acid (19.5 B.) at 10 C. and the diazo compound is coupled with a further 220 parts of m-aminophenylpyrazolone-3-carboxylic acid and 280 parts of sodium carbonate. The separated disazodyestuff is dissolved in water, converted at 10 C. into the diazo compound by adding 75 parts of sodium nitrite and 500 parts of hydrochloric acid (19.5 B.) and coupled with 205 parts of l-phenylpyrazolone-3-carboxylic acid and 280 parts of sodium carbonate. The triazodyestuff thus obtained is reduced at 70 C. with 420 parts of' crystallized sodium sulfide, separated by adding salt and dried. The dyestufl. corresponds in its free state to the following formula:

nmsQmrcoQ-smcm ll 110.0 N

and yields, when dyed on the fiber, diazotized and developed with p-naphthol, essentially yellower shades than the corresponding trisazodyestuif prepared from the condensation product of the formula:

IIIO:

which only differs from the first dyestuii by the absence of the negative radical SO2CH3.

We claim: 1. Cellulosic fibers dyed with a dyestuff of the general formula wherein G stands for'the radical of a yellow component of the group consisting of pyrazclones, acetoacetic acid arylamides, ketoles, 3. Cellulosic fibers dyed with a dyestufi. corphenol-o-carboxylic acids and combinations of responding in the form of the free acid to the pyrazolones with pyrazolones and of pyrazolones formula:

with other yellow components linked by azo I|\'02 groups, G being free from diazotizable amino 5 T groups, Y stands for a negativating substituent G 'C on selected from the group consisting of --CN, COOK NO2, halogen, SO2-- and -CO, the free valences'of the S02 and CO groups being connected to an organic radical, and the arylene 0 FRITZ SUCKFijIL radical belongsto the benzene series. HEINRICH CLINGESTEIN 2. Cellulosic fibers dyed with a dyestufi correspending in the form of the free acid to the 

